Azo dyes and methods for their preparation



Patented Feb. 25, 1936 UNITED STATES AZO DYES AND METHODS FOR THE RPREPARATION Emmet F. Hitch and Miles A. Dahlen, Wilmington, Del., andMartin E. Friedrich, Carneys Point, N. J., assignors to E. I. du Pont deNemours & Company, Wilmington, Del., a corporation of Delaware NoDrawing. Application July 27 1933, Serial No. 682,464

16 Claims.

This invention relates to the preparation of new azo dyes and-moreparticularly refers to the manufacture of water-insoluble azo dyeshaving the following general formula:

in which X represents an arylene nucleus.

It is an object of this invention to produce new azo pigments and dyes.A further object is to produce ice colors having good fastness to lightand washing. Additional objects will become apparent from aconsideration of the following description.

These objects are attained according to the herein described inventionwhich in its preferred embodiment comprises coupling a diazotizedarylamine of the benzene, diphenyl, naphthalene, diphenylamine,diphenylether, azobenzene, anthraquinone, or carbazole series, with atrifiuormethyl arylamide of 2-3-hydroxy naphthoic acid, arylamides ofthe benzene series giving, in general, most satisfactory results. Thesecompounds are chiefly ofi-mportance as ice colors, and when used forthis purpose the aforementioned components should be free fromwatersolubilizing groups, such as carboxylic and sulfonic acid groups.

The invention may be more readily understood by a consideration of thefollowing illustrative examples, in which the quantities are stated inparts by weight:

Example 1 40 parts of cotton piece goods well boiled and dried, wereimpregnated with the solution of the 2-3-hydroxy-naphthoyl derivative of3-aminobenzotrifluoride, prepared in the following manner:

8 parts of the 3-trifluor-methyl-anilide of 2-3- diazonium chloridefrom.2-5-dichloroaniline, prepared as follows:

16.5 parts of. 2-5-dichloroaniline were dissolved in a mixture of partsof hot water, and 58 parts of hydrochloric acid of 20 B. strength. 200parts of ice werethen added, followed by 8 parts of sodium nitrite (95%)dissolved in 30 parts of water. When the diazotizationwas finished thesolution was filtered; and just before coupling, the mineral acidity ofthe filtrate was neutralized with 45 parts of sodium acetate.

The dyed cloth was rinsed, soaped at the boil, again rinsed and dried.An orange dyeing, having good fastness properties to light and wash. ingwas obtained. The dye has the probable. formula:

Example 2 Cotton goods were impregnated with the 3'-trifluor-methyl-anilide of 2-3-hydroxy-naphthoic acid, as described inExample 1. The developer solution was prepared as follows: I

12 parts of ortho-dianisidine were dissolved in a mixture of 22 parts ofsulfuric acid of 66 B. strength and 60 parts of hot water. The solutionwas poured onto an excess of-ice, and the diazotization carried out witha solution of 7 parts of sodium nitrite dissolvedin 15 parts of water.Just before coupling, the mineral acidity was neutralized with chalk,and the solution was made slightly alkaline with sodium bicarbonate.

The dyed cloth was rinsed, soaped at the boil, again rinsed, and dried.In this manner a bright navy blue dyeing, having good fastness'to lightand excellent fastness to chlorine was obtained. The formula of the dyeis probably:

(|)OH: OCH:

OH OIFI OH OIFI Example; 3

hydroxy-naphtholc acid were pasted. up with 10 parts of ethyl alcohol,and then 10 parts of caustic soda of 35 B. were added. When thearylamide had dissolved completely, sufficient water was added to bringthe total volume up to 1600 parts.

The impregnated cloth was wrung out, and without drying, developedin asolution of the The cloth was impregnated as in Example 1 and wasdeveloped in a solution prepared as follows:

10 parts of 4-nitro-2-a1nino-anisole were dissolved in a mixture of 15parts of hydrochloric acid, (22 B. and,100 parts of boiling water.

The base was diazotized with a solution of 5 parts of hot water, anddried at fill-70 C. The material of sodium nitrite dissolved in 20 partsof water, was then 80% pure (M. W. 213).

with the addition of 160 parts of crushed ice for A printing paste wasmade up using the followcooling. When the diazotization was finished,ing materials: 7

5 the solution was filtered; and just before coupling, Parts 25 parts ofsodium acetate were added to neu- 2-3-hydroxy-naphthoyl derivative ofm-amtralize the mineral acidity. ino-benzotrifiuoride 3.2

The dyed cloth was rinsed, soaped at the boil, 1 Dried anti-diazotateobtained as aboveflu 2.7 again rinsed, and dried. In this manner abright Caustic soda (40 Be.) 3.0

10 red dyeing, having good fastness properties was Starch tragacanththickener 65.0

obtained. The dye has the probableformula: Water 26.1

()OHi 100.0 N= Cotton piece goods were printed with the paste,

then developed in the usual manner in a chrome- OH N01 OF| acetic acidbath. In this manner an orange print was obtained, due to the productionof the-dye ooNH-O of the probable formula:

Example 4 V 7 V i 42.6 parts of 4-chlor-2-amino-toluene were dis- I Qsolved in '76 parts of hydrochloric acid (37 and 100 parts of water. Thesolution was cooled to OH 01 (131% 0-5 C., by means of external cooling;and a solution of 21 parts of sodium nitrite dissolved in 50 CONE partsof water was added. The temperature was held at 05 C., by the additionof about 100 parts The following examples show the shades proof ice. Thesolution of the diazo salt was filtered, ducedby C up g other diazotizedarylamines comand run gradually into a mixture of 43 parts of monly usedas ice color bases, with a few of the piperidine-alpha-carboxylic acid,dissolved in 450 trifiuor-methyl-arylamides of 2-3-hydroxy-naphparts ofwater, at 5-l0 C. The alkalinity of the thoic acid suitable for useherein: I solution to phenolphthalein papers was maintained by theaddition of soda ash. When the coupling was finished, the solution washeated to ph i w deriv- Base. Shade L g t g- 40 0., and filtered. Saltwas then added until the diazoimino compound had precipitated. The oilwas separated, dried in a vacuum at 65 C., gfiffgg fi g m-ohlomniline-Scarlet y o 0 and utilized in application processes, such as the Do-5-igitro-l2-amino- Bin sii- Good. 4 following: lllSO re A printing pastewas prepared according to D0 itiiiiiie f Ream" verygood, the followingformula: Do i-glfihgg-i-DHIO- Scarlet Verygood. Parts Do 4-4-diamino-di-B1ue Good A dry mixture of 4-chlor-5-trim d fiit riifiiii d Orange FairFair, 3.2 parts of the 2-3-hydroxy-naphthoyl flupro-methyldelgvative ofmamino'benzotrifiuoride i igi j 2-? -dichloroani Orange..- Fair Fair. annt. 3.0 parts of the diazoimino compound ob- Do 2 -3561 r ii i Poor Goodr tamed as above Do p-tgalyialifiggo-ni- Scarlet Poor Good.causticsodawB-i 3.0 no M amin. N... vt m 6......

Starch tragacanth thlckener 65-0 Do g g t gfi gg; 5m Good Fain Water 25zoylamino-2-a blue.

diethoxyben- Cotton piece goods were printed with the print- It is to beunderstood that numerous mm.

ing paste, then developed by subjecting t0 the ines, other than thosedisclosed above,- may be a t of live Steam containing the Vapors 0fdiazotized and coupled according to the present tic acid. In this mannerthe pattern was develinvention As previously mentioned arylamims so d asa red dyeing. having good fastness wof the benzene, diphenyl,naphthalene, diphenylerties. The new color has the probable formula;ine, diphenyl-ether, azobenzene, anthraquin- OH one or carbazole seriesare preferable, although H the invention is by no means limited thereto.

. Q Likewise, these arylamines may have numerous V l V 74 well knowngroups substituted thereon. Where OH 1 CF they are to be used in theproduction of ice colors I it is imperative that they contain nowater-solu- CONE-O bilizing groups. However, with the exception of thesewater-solubilizing groups they may have one or more of the various wellknown substituents substituted thereon. Among these substituents2-5-dichloroaniline was diazotized, and conmention may be made of thehalogen, alkyl, a1-

verted to the sodium salt of the anti-diazotate by koxyl, nitro,acylamino and trifluoro-methylthe method described in U. S. P. 531,975.The groups. I

76 product was recrystallized from a small amount Manytrifluo-ro-methylarylamides of 2-3-hy- Example 5 droxy-naphthoic acidmay be used in place of those selected in the illustrative examplespreviously given. When selecting these arylamides it is advisable tochoose arylamides of the benzene series. However, it is not intended tolimit this invention to arylamides of the benzene series, sincearylamides of the other commonly known aromatic series may likewise beused with good results. Among the arylamides which are suitable for usein this connection attention. may be directed to the following:

Arylamide of 2-3-hydromy-naphthoic acid 2-Trifluoromethyl-anilide4-Trifluoro-methyl-anilide Z -Methyl- -itrifluoro -methyl -anilide 2',5-Di-trifluoro-methyl-anilide 2'-Chloro-5-trifluoro-methyl-anilide2-Trifiuorornethyl-4'-methoxy-anilide2-Trifiuoro-methyl-4'-ethoxy-anilide 2 Methoxy 4trifiuoro-methyl-fi-methoxyanilide These arylamides may also have one ormore nonwater-solubilizing groups substituted thereon. Examples of a fewof such substituents are halogen, alkyl and alkoxy groups. Wheretrifluormethyl-arylamides are mentioned throughout the presentspecification and claims it is to be understood that this term includesthe presence of more than one trifluor-methyl group on the arylamidenucleus. A method of making these substances is described in Patent No.1,982,661, wherein are claimed the intermediates which are used hereinin the manufacture of dyes.

The compounds forming the subject matter of this invention may beproduced as pigments or dyes. When produced as dyes they may be utilizedto impart color to textile materials according to various well knownprocedures. Among these dyeing processes mention may be made of V thefollowing:

(1) Textile material may be padded with the arylamides heretoforedescribed, and then developed in diazo salt solutions prepared fromarylamines selected according to the instructions previously given.

(2) The material may be padded with the arylamines and then printed withpastes containing diazo salts obtained from the arylamines.

(3)The arylamides may be mixed with antidiazotates (nitrosamines)derived from the described arylamines. Textile fibers are thenimpregnated with pastes containing such mixtures and subjected to theaction of weak acids.

(4) The arylamides may be mixed with watersoluble diazoimino compoundsderived from the arylamines coming within the scope of this invention.Textile fibers are then printed with pastes containing such mixtures andsubjected to the action of heat and weak acids resulting in theformation of the new dyes on the material.

The products described herein are valuable either as pigments or dyes.They impart to textile materials bright shades which are usually ofexcellent fastness to washing, lightand chlorine. These shades are veryattractive and are quite desirable from a commercial point of View.

As many apparently widely different embodiments of this invention may bemade without departing from the spirit and scope thereof, it is to beunderstood that the invention is not limited to the specific embodimentsthereof except as defined in the appended claims.

We claim:

1. A process for producing azo dyes which comprises coupling adiazotized arylamine with a trifluor-methyl-primary of 2-3-arylamidehydroxynaphthoic acid.

2. The process of claim 1 wherein the components are free fromcarboxylic and sulfonic acid groups.

3. A process for producing water-insoluble azo dyes which comprisescoupling-a diazotized arylamine selected from the group consisting ofarylamines of the benzene, diphenyl, naphthalene, diphenylamine,diphenylether, a z o b e n z e n e, anthraquinone and carbazole series,with a trifiuor-methyl-anilide of 2-3-hydroxy-naphthoic acid.

4. A process for producing water-insoluble azo dyes which comprisescoupling a diazotized arylamine selected from the group consisting ofarylamines of the benzene and naphthalene series with atriiiuor-methyl-anilide of 2-3-hydroxynaphthoic acid.

5. A20 dyes having the following general formula:

in which X represents the residue of a trifluormethyl-anilide.

6. The dyes defined in claim 5 wherein the components designated as Aryland X are free from sulfonic or carboxylic acid groups.

'7. Water-insoluble azo dyes having the following general formula:

in which R represents the residue of an arylamine of the benzene,diphenyl, naphthalene, diphenylamine, diphenylether, azobenzene,anthraquinone or carbazole series, and X represents the residue of atrofluor-methyl-anilide.

8. Water-insoluble azo dyes having the following general formula:

in which R represents the residue of an arylamine of the benzene ornaphthalene series. 4

9. The method of making an azo dye whic comprises coupling a diazotizedaniline with one of a group of compounds consisting of a halogeno-, analkyl-, and an alkoxy tzifluoromethylanilide of 2,3-hydroxy-nap hthoicacid.

10. A water-insoluble azo dye being the product of coupling a diazotizedaniline with one of a group of compounds consisting of a halogeno-, analkyl-, and an alkoxy trifluoromethyl-anilide of 2,3-hydroxy-naphthoicacid.

11. A process for producing azo dyes which comprises coupling adiazotized arylamine with a trifluor-methyl-anilide of2,3-hydr0Xynaphthoic acid.

12. A process for producing azo dyes which comprises coupling adiazotized arylamine free from water-solubilizing substituents with atrifiuor-methyl-anilide of 2,3-hydroxy-naphthoic acid free fromwater-solubilizing substituents.

13. A process for producing an azo dye which comprises coupling adiazotized arylamine with one of a group of compounds consisting of ahalogeno-, an alkyl-, and an alkoxy trifiuoromethyl arylamide of2,3-hydroXy-naphthoic acid.

14. An azo dye described by the structural formula Aryl-N=ITI CONH-XEMMET F. HITCH. MILES A. DAHLEN. MARTIN E. FRIEDRICH.

CERTIFICATE OF CORRECTION.

Pate t No- 2,051,65i.

.EMMET F. HITCH, ET AL.

It is hereby certified that error appears in the printed. specificationof the above numbered patent requiring correction as follows: Page 5,second column, strike out lines 1 to 4 inclusive, comprising claim 1,and insert instead the following:

1. A process for producing azo dyes which comprises coupling a.diazotized arylamine with a trifluor-methyl primary erylamide of2-3-hyclroxy-nephthoic acid. and that the said Letters Patent should. beread with this correction therein that the same may conform to therecord of the case in the Patent Office.

Signed and sealed this 5th day of May, A. D. 1936.

Leslie firazer Acting Commissioner of Patents.

February 25, 1956.

